Product for producing effervescing carbonated beverages



Patented Mar- 8, 1949 PRODUCT FOR PRODUCING EFFERVESCING CARBONATEDBEVERAGES Henry J. Goroica, Prospect Heights, 11]., and Leo J. Novak,Decatur, Ind., assignors to Fearn Laboratories, Inc., Franklin Park,111., a corporation of Illinois No Drawing. Application May 17, 1947,Serial No. 748,838

8 Claims. 1

This invention pertains to a chemical compound or product for use inproducing carbonation and eifervescence in liquids, as where a liquid isfor beverage purposes. The subject matter of this application has beendescribed in part and has been claimed in my prior application SerialNo. 569,437, filed December 22, 1944, which has now become abandoned, ofwhich application this is a continuation in part. The process by whichthe product is produced in commercial quantities and in an efficientmanner, is described and claimed in my copending application Serial No.8018, filed February 12, 1948, as a continuation in part of an earlierflied application.

Efiorts have heretofore been made to produce efl'ervescing carbonatedbeverages by introducing into the beverage liquid a solid substance inpowdered or tablet form which would dissolve in p the liquid and releaseor produce carbon dioxide which would bubble up through the liquid so asto produce efiervescence and would be" partially absorbed by the liquidto produce carbonation of the same.

None of the products heretofore employed for this purpose have, so faras we are aware, met with any substantial degree of commercial favor,because of the presence in the resultant beverage of one or more of thefollowing undesirable characteristics:

(a) The beverage was unpalatable.

(b) It was excessively acid or excessively alkaline.

(c) Th amount of carbonation was insumcient.

(d) The rate of carbonation was unsatisfactory, i. e., the CO: would beliberated too quickly, caus ing a flash foaming of the beverage, or itwould be liberated too slowly, so as to require too long a wait beforethe beverage would be sufllciently carbonated to be palatable.

(e) The clearness of the beverage was impaired,

so that it presented a murky or translucent and,

therefore, unattractive appearance.-

The primary purpose of our present invention is to provide a. productfor carbonating and producing effervescence in beverages which willneither possess nor produce in the beverage into which it is introducedany of the above mentioned undesirable characteristics, but, on thecontrary, when added to a liquid will produce a carbonated aqueoussolution neither unpleasantly alkaline nor acid, but closely resemblingin taste ordinary carbonated water or soda water. Furthermore, thebeverage produced by the employment of our product will besatislactorily clear and sparkling in appearance, the rate ofcarbonation will be such that an initially rapid production of CO: willbe caused so as to quickly produce carbonation and eflervescence-withoutmomentary flashing or foaming, and which will produce a continued andretarded carbonation and effervescence, thereby insuring thepalatability and attractiveness of the beverage for a considerableperiod of time.

The produce comprises a mixture of solid material in granular andpowdered form, the material consisting of a carbonating agent or sourceof carbon dioxide and an acid adapted to react with the carbonatingagent in the presence cf water to liberate the carbon dioxide and enablethe solid residue to dissolve so as to leave no sediment in the bottomof the glass.

The carbonating agent or source of carbon dioxide employed in ourproduct is the dry compound or compounds formed by re-acting, undercontrolled low temperature and controlled pressure, a mixture of (1)water, (2) an organic, non-reactive, non-polar, water miscible liquidsuch as methyl, ethyl or propyl alcohol, ethylene glycol, propyleneglycol, acetone, glycerine or other organic compound (otherwisedescribed as a solvent of the class of saturated alcohols derived from1,2 or 3 carbon atom compounds) miscible with water and non-reactingwith amino acid or amino acids, divalent metallic hydroxide and carbondioxide in the presence of water, (3) a non-toxic amino acid or amixture of amino acids either natural, synthetic, or from hydrolysa'tessuch, for instance, as glycine, alanine or glutamic acid, mixtures ofamino acids, or solu ble, neutral protein hydrolysates such for instanceas soluble, hydrolyzed neutral casein, and all of which, briefly, may bedescribed as an amino acid or acids having a free primary amino group,(4) a molecular reacting equivalent of a nontoxic divalent metallichydroxide such as calcium hydroxide, magnesium hydroxide or ferroushydroxide, and (5) sufllcient carbon dioxide to produce the desiredcarbamino salt type of carbonating compound or compounds.

The production of a carbamino salt type of compound or compounds fromthese materials is effected in accordance with our method in thefollowing manner.

An aqueous solution, either saturated, or partially saturated is firstprepared by mixing a weighed'amount of the amino acid or acids forexample glycine or glutamic acid with a measured volume of cold water.To this solution mixture is then added a suitable organic solvent suchas above indicated, or a mixture of two or more of these compounds,until preferably 66%% organic solvent or solvents and 33 /372, water isobtained. In this solvent a A molar solution of the amino acid or aminoacids liquid mixture is prepared. A few drops of phenolphthaleinindicator are now added. While the proportions of water and-solvent asgiven above are preferred the proportions may be varied over aconsiderable 3 range i. e. water to 50% and solvent 90% to 50%respectively.

aaoaoca A molecular reacting equivalent or divalent basic metallichydroxide, for example calcium hydroxide, is then weighed and made intoa thick liquid suspension with a minimum amount of the 66%% organicsolvent or solvents-33%% water solution, using the above statedpreferred proportions of water and solvent. This liquid suspension isthen added to more of the 66%% organic solvent or solvents-33 /3% watermixture of amino acid or acids until the latter mixture is pink tophenolphthalein indicator. Thissolution mixture is now cooled in aclosed pressure container with suitable stirring apparatus to 0-20 C.,stirred, and carbon dioxide is passed in at a slow rate until thesolution mixture just loses the pink color. ganic solventwater-solutionmixture is added with stirring until the reacting mixture turns adefinite pink again. More carbon dioxide is again added as previouslydescribed until the pink color again just fades. This process is repeated until all the basic hydroxide-organic solvent-water mixture isadded. Carbon dioxide at higher pressures for example 30-40 lbs. per,

square inch is now passed in until no more is absorbed.

The final reacted mixture is now removed from the reaction vessel byblowing it out with carbon dioxide under pressure. It is filtered cold,washed with a low boiling point, miscible, nonreactive, non-polar, cold,organic solvent if necessary (for example if ethylene glycol was used in66%% concentration in the reaction, the residue of carbamino compound orcompounds on the filter can be washed with acetone) then gently air orvacuum dried at a low temperature, for example 50 to 80 C.

The formulas of the compounds formed by these materials, describedabove, are substan-.

tially of the following type: U

NHICO; R NHiCOsXCOiNH: R RCH NH-COO X=Ca++ Mg++ Fe++ R'=Hydrogen or anorganic radical of suitable character, for example: CH3, CzHs, Cal-I1,C4Ha,

etc.

Some carbonate of calcium may be formed, depending upon such factors as,for example, solvent and reaction rates. The reactions occurring duringthe aforementioned method of preparation are represented substantiallyas follows:

(l) R NHaCO:

In these reactions, x c Mg-i-"i- R=An organic radical or hydrogen forexample,

CH3, Cal-I5, C3H7, CiHa, CsHu, CsHsCI-Ia, COOH (CH2) 2, COOHCHz, etc.

More basic hydroxide-or- CsHn, CsI-IsCI-Is, COOH(CH2)2, COOH CH2,

' of the final products of reaction.

A typical illustration of our method is exempliiied by the followingprocedure.

To 4.5 liters of pure water is added 281 grams of glycine (amino-aceticacid), the mixture is stirred and 10.5 liters of ethyl alcohol is added.280 grams of pure calcium hydroxide, preferably free of calciumcarbonate is mixed into a minimum of 33%% water and 66%% ethyl alcoholto form a thick liquid suspension. This calcium hydroxide liquidsuspension is'how added to the amino-acetic acid-water-ethyl alcoholmixture containing a few drops of phenolphthaiein until a distinctpink-red color is obtained. This mixture is now cooled to 0-10 C., in asuitable closed pressure reaction vessel equipped with stirrer. Whilethis liquid is being a ture is then added with stirring until thesolution mixture turns pink again. More carbon dioxide is again passedin until the color just fades again. This process is repeated until allthe calcium hydroxide has been added and the pink color'ofphenolphthalein has just faded due to carbon dioxide absorption. Carbondioxide is then passed in at from, for example, 30-50 pounds per squareinch until no more is absorbed. The mixture is then removed from thereaction vessel preferably by blowing it out with carbon dioxide andfiltered while cold, washed with cold acetone or 95% ethyl alcohol toremove most of the water, and gently vacuum dried at for example, atemperature of 50-70 C., and 25-30 inches vacuum, or it can be air driedat for example 50-80 C.

Preferably the ground material is then graded into granular sizes bybeing passed through sieves of selected mesh sizes. The thus gradedgranules may then be employed in selected proportion as constituents ofthe product for producing effervescent carbonated beverages disclosed inour aforementioned co-pending application.

A carbamino salt type of compound produced in accordance with our methodabove disclosed includes or carries a substantial amount of carbondioxide in condition to be liberated for eilervescent and carbonationpurposes by subjection to the action of a suitable acid in the presenceof water. Furthermore, the solid constituents of the compound arereadily soluble in water, consequently, when the compound is employedfor beverage making P p ses, the entire composition is either dissolvedin the water or liberated as carbon dioxide so that no objectionableresidue is left in the bottom of the glass.

The acid component of our improved product is a solid non-toxic acid oracids adapted to react with the above described carbamino salt type ofcompounds in the presence of water to produce carbon dioxide and anon-toxic solution As examples of the acids we may present: Citric,malic, tartaric, succinic, fumaric acids. One of these acids or amixture of them is dried, sieved to suitable particle size, for example40-80 mesh, and mixed with a predetermined amount of the dry, sieved,mesh (or higher) carbamino salt type of compound or compounds, as hereindescribed. When this mixture is thrown into water, the acid dissolves,and reacts with the dioxide, which may saturate the solution;

for example citric acid may react with calcium glycine carbaminocompounds as follows:

cmcoon mnco. CoCOaNE:

-COOH 3c CHzC 0 Oil Citric acid Hi0 CH1 -0 CO:CIICO| Calcium glycinecarbamino double molecule, hydrated scrnnrncoon zomonnoo, 600, one

Glycine JEhOOOH 00 Ca Citric acid Calcium carbamino glycine. nothydrated acrnNmooon 300, C8r(CsHi01)| Calcium citrate Our productconsists of a dry mixture of the carbamino salt type of compound orcompounds, for example, calcium carbamino salts of glycine and acid oracids, for example, citric or malic, which is normally stable'in theabsence of moisture and which can be packaged and stored for indefiniteperiods or at least so long as it is not subjected to suflicientmoisture to induce a chemical reaction between the component carbon tincompo d or compounds and acid or acids. The properties of the componentsin the final dry mixture of the product may vary considerably, dependingupon what final pH is desired in the final aqueous effervescingsolution. The proportions of the components in the final mixture of theproduct also may vary considerably, but we have found that the mostsatisfactory results have been obtained from a product consisting of amixture in substantially the following proportions:

Per cent Calcium carbamino salt of amino-acetic acid 50-60 Acid ascitric acid 50-40 Both the carbonating compound and the solid acid areof granular formation and the rate of carbonation resulting from achemical reaction of these components in the presence of water may beregulated by grading and proportioning the sizes of the granules of.both components of the product. slower the chemical reaction and,consequently, the slower the rate of carbon dioxide liberation in thebeverage. If, on the other hand, the granules be of small size, forinstance, substantially powdered, the velocity of the chemical reactionwill be increased so that the rate of evolution of carbon dioxide in theliquid will be stepped up, but the duration of carbon dioxide evolutionand of carbonation will be correspond ingly diminished. The mostsatisfactory results are attained by employing graded sizes of granulesin predetermined proportions so that a rapid chemical reaction andliberation of carbon dioxide will result from the smaller particles soas to give a quick initial carbonation and efiervescence, and a retardedand prolonged reaction will result from the larger particles, thusproducing in the beverage a prolonged carbonation and eflervescencewhich prevents the beverage for a considerable period from becoming flatand stale.

Where one employs a carbamino salt type of compound as the carbonatingagent for reaction with a suitable acid to produce the requisite car-The larger the granules, the

bon dioxide, 9. highly palatable beverage strongly resembling ordinarysoda water is obtained by mere introduction of our improvedproduct intoclear unflavored water. The beverage thus produced has a slightly acidtaste of the carbon dioxide and, if the glycine carbamino compound isused, a slightly sweet taste derived from the glycine utilized in theproduction oi carbamino compound.

It will be obvious that any desired flavor in the form of oils, sugarsor juices maybe added to make a beverage having any desired flavor. The

carbonation of such a beverage resulting from the employment of ourproduct will be sufficient for palatability and will continue so as toprevent staleness of the beverage for a considerable period of time. Ourproduct is completely soluble in water, so as to leave no sediment inthe glass and it imparts neither excessive acidity nor alkalinity to thebeverage, but results in a beverage which has a pleasing, slightly acidtaste.

We claim:

1. A dry, solid, water-soluble product, chemically stable in the absenceof moisture, for the production of eiiervescence in and carbonation of abeverage liquid when introduced into such beverage liquid, comprising, acarbamino compound derived from a reacted mixture of (1) water; (2) asolvent of the class of saturated alcohols derived from one, two orthree carbon atom compounds miscible with water and non-reacting with anamino acid, divalent metallic hydroxide and CO2 in the presence ofwater; (3) non-toxic amino acid having a free primary amino groupselected from the group consisting of glycine, alanine, glutamic acidand mixtures thereof, and soluble, neutral protein hydrolysates such assoluble, hydrolyzed neutral casein; (4) a molecular reacting equivalentof a non-toxic divalent metallic hydroxide selected from the groupconsisting of calcium hydroxide, magnesium hydroxide and ferroushydroxide; and (5) carbon dioxide; in mechanical combination with asolid, nontoxic acid selected from the group consisting of citric,tartaric, malic, succin-ic and fumaric acids.

2. A dry, solid, water-soluble product, chemically stable in the absenceof moisture, for the production of effervescence in and carbonation of abeverage liquid when introduced into such beverage liquid, comprising, acarbamino salt derived from a reacted mixture of: (1) water; (2) asolvent of the class of saturated alcohols derived from one, two orthree carbon atom compounds miscible with water and non-reacting with anamino acid, divalent metallic hydroxide and CO2 in the presence ofwater; (3) non-toxic amino acid having a free primary amino groupselected from the group consisting of glycine, alanine, glutamic acidand mixtures thereof; (4) a molecular reacting equivalent of a non-toxicdivalent metallic hydroxide selected from the group consisting ofcalcium hydroxide,-magnesium hydroxide and ferrous hydroxide; and (5)carbon dioxide; in mechanical combination with a dry, solid non-toxicacid selected from the group consisting of citric acid, tartaric acidand malic acid.

3. A product as defined in claim 1 in which the proportions are from 50%to 60% of carbamino compound and 50% to 40%, respectively, of acid.

4. A product as defined in claim 2 in which the proportions are from 50%to 60% of carbamino salt and 50% to 40%, respectively, of acid.

5. A product as defined in claim 1 in which the carbamino compound is acarbamino salt of amino-acetic acid and the proportions are from 50% to60% of salt and 50% to 40%, respectively, of acid.

6. A product as defined in claim 2 in which the carbamino salt is acarbamino salt of aminoacetic acid and the proportions are from 50% to 560% of salt and 50% to 40%, respectively, of acid.

7. A product as defined in claim 1 in which the granules of the compoundand acid are or predetermined graded sizes whereby the release of carbondioxide from the product in the presence 10 REFERENCES CITEDThe'following references are of record in the me or this patent:

8 UNITED 8TA'I'ES.PATENTS Number Name Date 284,464 Mlchaelis Sept. 4,1883 342,624 Michaells May 25, 1886 1,948,002 Mittasch et a] Feb. 20,1934 OTHER REFERENCES Siegfried et a1. (Gen), 188,005, Sept. 6, 1907,Zeit fur physlol. chem., vol. 44.

Siegfried et al., Zeit fur physio]. Chem., vol. 54. pages 423-36 (1908).

Blayd, Biochem. Journal, vol. 27, pages 1838-48 (19 Stadie et a1., Jour.Blol. Chem, vol. 112, pales Majer, Chem. Abstracts, vol. 23, page 728(1929) Spothr et al., Chem. Abstracts, vol. 20, Dale 2181 (1926).

Certificate of Correction Patent No. 2,463,962. March 8, 1949.

HENRY J. GORCICA ET AL.

It is hereby certified that errors appear in the printed specificationof the above numbered patent requiring correction as follows:

Column 2, line 5, for the word produce read product; column 3, line 3,for equivalent or read equivalent of; column 5, line 13, for thatportion of the formula reading NCOO read NHCOO;

and that the said Letters Patent should be read with these correctionstherein that the same may conform to the record of the case in thePatent Offioe.

Signed and sealed this 30th day of August, A. D. 1949.

THOMAS F. MURPHY,

Assistant Oommissioner of Patents.

Certificate of Correction Patent No. 2,463,962. March 8, 1949.

HENRY J. GORCICA ET AL.

It is hereby certified that errors appear in the printed specificationof the above numbered patent requiring correction as follows:

Column 2, line 5, for the Word produce read product; column 3, line 3,for equivalent or read equivalent of; column 5, line 13, for thatportion of the formula reading N-COO read NHOOO;

and that the said Letters Patent should be read with these correctionstherein that the same may conform to the record of the case in thePatent Office.

Signed and sealed this 30th day of August, A. D. 1949.

THOMAS F. MURPHY,

Assistant Commissioner of Patents.

